JPH0130915B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a hybrid bipolar electrode (heterogeneous bipolar electrode).
The present invention relates to the production of metals and metalloids by cathodically dissolving them in an electrolytic cell having a series of bipolar electrodes. The production of non-ferrous metals in general and so-called reactive metals in particular currently relies on (a) discontinuous chemical processes, (b) electrowinning cells with insoluble electrodes, (c) anodic dissolution of compounds and cathodes of metals. This is done by precipitation. Discontinuous chemical methods require intensive labor and
Furthermore, metals having the purity specifications currently required are not produced. The use of conventional electrolytic cells is limited to metal compounds that have sufficient solubility in the electrolyte. Anodic dissolution of metal compounds usually results in low yields, which are unacceptable for industrial equipment processes. The operation of an electrolytic cell having a terminal cathode, on which the metal is precipitated, and an insoluble terminal anode, on which the element or compound initially associated with the metal and constituting the raw material is precipitated, was known to those skilled in the art. . It has been known to perform electrowinning using a pair of electrodes, a cathode and an insoluble anode, to reduce the metal concentration in the electrolyte. An object of the present invention is to provide a method for producing a highly pure metal or metalloid from a metal or metalloid compound, and the present invention provides a method for producing a highly pure metal or metalloid from a metal or metalloid compound, which is a starting material containing a low-solubility or insoluble metal. Use electrolytes containing The present invention achieves this objective. The subject of the invention is a method for producing metals or metalloids from compounds of metals or metalloids using an electrolytic cell consisting of an anode, a cathode and an electrolyte extending from the anode to the cathode. a plurality of metals formed by charging said electrolytic cell with an auxiliary metal or mixture of metals in solid or liquid state, in electron conductive contact with the cathode and solubilized in the electrolyte by direct cathodic reduction; (b) supplying the compound to be solubilized to the electrolytic cell while passing an electric current through the electrolytic cell; and in electron conductive contact with the cathode portion of each of said charges for direct cathodic reduction of the metal or metalloid of said compound on said cathode portion and the transfer of metal ions from the anode portion of each charge to the electrolyte. and (c) circulating an electrolyte in a closed circuit including the electrolytic cell and the electrowinning cell, and electrolytically separating the metal or metalloid to be produced in the electrolytic cell from the electrolyte. This is a method for producing a metal or metalloid. The use of the electrochemical mechanism of the present invention to produce any metal or metalloid by operation with a hybrid bipolar electrode has never before been proposed. In other words, cathodic dissolution of metal compounds at the same time as, but separate from, cathodic dissolution of metals has never previously been possible. One of the main features of the series electrochemical system involving hybrid bipolar electrodes suitable for the production of metals and metalloids, which is the object of this invention, is that they generally exhibit low solubility when acted upon chemically only. The fact is that high current efficiency electrochemical dissolution of compounds, including reactive metal compounds, can be performed. The hybrid bipolar electrode is any electronic conductor of any shape and has a surface portion immersed in an electrolyte. One of the surface parts is used for electrochemical half-reactions such as redox reactions.
redction), and the electrochemical half-reaction is not a reverse reaction to the electrochemical half-reaction occurring at the other position of the surface portion, and is the same as the electrochemical half-reaction occurring at the other position. It's a different reaction. For example, anodic dissolution (oxidation) of metal is performed on the side surface (front side) of a solid electrode plate that is vertically immersed in an electrolytic solution, while the metal to be manufactured is oxidized on the other side surface (back side). It can be seen that a reduction of the compound takes place, so that this metal can be different from the metal dissolved on the other side (front side) of the bipolar electrode. This latter metal is called an auxiliary metal. It is also possible that instead of anodic dissolution of the metal, oxidation and gas evolution can occur on the side. It is also possible that the reduction of the metal compound is only a partial reduction, for example of a ring element of a higher oxide (dioxide) to a lower oxide (monoxide). In this case, an electrolytic solution is selected that can act by chemical reaction on the low valence compounds that have just been produced on the electrode surface. From one to any number of hybrid bipolar electrodes can be arranged in series with their appropriate spacing. A series electrochemical circuit is achieved by introducing a positive terminal electrode, soluble or insoluble, ie responsible for gas generation or metal dissolution. The negative terminal electrode is a compound (e.g. oxide),
Electrodeposition of metal coming from the reduced cathode side of the hybrid bipolar electrode can be accommodated.
The negative end electrode is also responsible for the cathodic dissolution of the metal compound and itself to be produced. In working with bipolar electrodes of suitable geometry, the negative end electrode need not be placed in linear series with all other electrodes. By the mechanism shown above, a larger amount of the compound can be dissolved than the amount of metal deposited on the negative terminal electrode. Therefore, one cathode on which excess dissolved metal can precipitate and an oxidation reaction can occur.
An electrowinning system consisting of one preferably insoluble anode must be introduced into the electrolytic cell. The electrowinning system can also be installed in a separate electrolytic cell separate from the electrolytic cell with the hybrid bipolar electrode. However, in this case, the condition is that the electrolytic solution is exchanged or circulated between the two types of electrolytic cells. The electrowinning cell can also be connected to a separate DC power source for control independently of the power source used for the electrolytic cell containing the hybrid bipolar electrode. FIG. 1 is a schematic diagram of an embodiment of the present invention for electrolysis and electrowinning of titanium from titanium dioxide on mercury. FIG. 2 is a schematic diagram of an embodiment of the present invention for electrowinning of lead from sulfides. FIG. 3 is a cross-sectional view of the electrolytic cell taken along the - line in FIG. 4, and in this electrolytic cell,
According to the invention, a liquid metal having a density greater than that of the electrolyte is used, and the cathodic dissolution of the liquid or gaseous compound is carried out simultaneously with the electrowinning of the metal. FIG. 4 is a sectional view taken along the - line in FIG. 3. FIG. 5 is a cross-sectional view of the electrolytic cell taken along the - line in FIG. 6, and in this electrolytic cell,
According to the invention, cathodic dissolution of the liquid or gaseous compound of the metal to be produced is carried out. FIG. 6 is a sectional view taken along the line - in FIG. 5 of FIG. 6; FIG. 7 is a cross-sectional view of the electrolytic cell taken along the - line in FIG. 8, and in this electrolytic cell,
According to the invention, cathodic dissolution of the solid compound of the metal to be produced is carried out. FIG. 8 is a sectional view taken along the - line in FIG. 7. FIG. 9 is a cross-sectional view of an electrolytic cell in which, according to the invention, cathodic dissolution of solid compounds is carried out when the liquid metal has a density less than that of the electrolyte. FIG. 10 is a cross-sectional view of an electrolytic cell in which, according to the invention, the metal to be produced is Cathodic dissolution of the compound is performed. FIG. 11 is a cross-sectional view of an electrolytic cell for cathodic dissolution and simultaneous metal electrowinning of the compound when the anodic reaction is gas evolution and the function of the auxiliary metal is supported by a solid electronic conductor. be. FIG. 12 is a cross-sectional view along line XII--XII of FIG. 13 of an electrolytic cell consisting of a stack of horizontal hybrid bipolar electrodes. FIG. 13 is a cross-sectional view of the stack of FIG. 12 along the - line. FIG. 14 illustrates a simplified flowchart of an electrolytic titanium production apparatus embodied in accordance with the present invention. Since then, we have used heterogeneous bipolar electrodes.
electrode) is also indicated by the acronym HBE. In FIG. 1 of the schematic diagram illustrating the electrowinning of titanium on mercury, a metal compound, namely dioxide, is continuously introduced into the electrolytic cell and comes into contact with the cathode side 11 of the HBE 12. The cathodic half-reaction uses up a set of electrons that are free and come from the anodic side ₁₃ of the HBE (where the other ^half -reaction takes place) ^; The reduction of a substance to a lower oxide, such as a monoxide. The two parts of the HBE are separated by a wall 14. The electrolyte CA17 reacts with the monoxide by a chemical reaction that forms a metal compound, which is soluble in the electrolyte itself, according to the following reaction format: TiO+2CA=TiA ₂ +C ₂ O. The half-reaction that takes place on the anode side 13 of the HBE 12 can be any oxidation reaction that is compatible with the species present in the electrolyte. For example, the oxidation of a considerable amount of metal (already produced) can be carried out according to the reaction: Ti=Ti ⁺⁺ +2e ^- , or a reaction of the form: Me=Me ⁺⁺ +2e ^- Accordingly, other metals (auxiliary metals) can be oxidized. The auxiliary metal (in this case mercury) is co-deposited with the metal to be produced on the terminal electrode 15 and then separated from the metal. Soluble anode 16
is composed of mercury. A pair of electrodes, a cathode 18 and an insoluble anode 19, are used to electrowinning the metal excessively dissolved by the HBE 12. The metal is deposited on the electrowinning cathode at a rate such that the electrolytic operation can be kept stable. To better explain the embodiment of the present invention for the production of non-ferrous metals, the electrowinning of lead is illustrated in FIG. 2 of the schematic diagram. A metal compound, ie, a sulfide, is continuously introduced into the electrolytic cell and brought into contact with the cathode portion 21 of the HBE 22 . Metal lead is continuously dissolved in the anode part 23. The HBE itself can also be made of molten lead. Electrolyte 27 can be an aqueous solution or a molten salt forming a soluble lead compound. In this case, no reduction of the compound containing the metal to be produced takes place, but instead an electrochemically promoted dissolution of the compound takes place at a rapid dissolution rate.
This is one objective of the invention. A pair of electrodes, a cathode 28 and an insoluble anode 29, is used for electrowinning of metals and elemental sulfur. Generally, elements (or compounds) that were originally part of the raw material containing the metal to be produced are formed at the anode of electrowinning. Oxygen is evolved when working with metal oxides, chlorine when using chlorides, and sulfur when using sulfides. The same applies to other compounds. By selecting suitable auxiliary metals, the metal to be produced can be obtained by fractional crystallization. When working with molten salt-based electrolytes, or mixtures thereof, it is useful to use low melting point metals as auxiliary metals. This liquid metal can be in a horizontal geometry with respect to the HBE itself. The density of the metal forming the electrodes determines the geometry of the electrolytic cell with respect to the electrodes at the bottom or at the surface. Examples of auxiliary metals include alkali metals or alkaline earth metals such as Li, Na, K, Mg, Ca, Sr, and Ba.
and low melting point metals of Group B: Zn, Cd, Hg;
Group a: Al, Ga, In, Ti; Group A: Sn, Pb; A
Family: Sb, Bi. The horizontal arrangement is advantageously applied to aqueous or non-aqueous solutions using amalgam or mercury compounds as auxiliary metals for the hybrid bipolar electrode. On the other hand, when using an auxiliary metal that is solid under operating conditions, the metal compound is applied in the form of a paste onto a grid structure made of the auxiliary metal and pressurized to produce an HBE. Electrical connection with the metal compound can be ensured. A controlled atmosphere is useful for the electrochemical methods described above. Particularly when producing reactive metals, it is necessary to have an inert gas, such as argon or helium, above the electrolyte.
Gases with reducing properties, such as hydrogen, are furthermore advantageous. When the anodic reaction that takes place at the terminal electrode, the anode side of the HBE, and the anode of the electrowinning system is a gas generation reaction, the pressure above the electrolyte should be kept below atmospheric pressure, especially
It is also beneficial to maintain between 10 mmHg and 200 mmHg to facilitate the reaction. As the electrolyte, a number of solutions are used whose essential feature is solubility for the metal- or metalloid-containing compounds produced either by reaction on the HBE or by reaction with the electrolyte itself. be able to. For example, some solutions include fluoroboric acid, sulfamic acid, and methylsulfonic acid, either alone or as a mixture, and either as an anhydrous molten salt or as an aqueous solution, and organic solvents such as acetonitrile, butyrolactone. , dimethylformamide, dimethylsulfoxide, ethylene carbonate, ethyl ether, methylformate, nitromethane, propylene carbonate, tetrabutylammonium iodide. Electrolytes based on molten salts include the following alkali metals and alkaline earths: Li, Na, K,
The chlorides and fluorides of Rb, Cs, Mg, Ca, Sr, Ba can be used either singly or as a mixture with a melting point below 825°C.
Some of the electrolytic baths used are shown in the table and the average temperature at which the electrolysis is carried out.

【table】

【table】

Table: For the production of reactive metals, titanium dioxide, titanium tetrachloride, zirconium dioxide and zirconium tetrachloride are very stable materials under many conditions. According to the invention, the electrochemical reduction of the compound is simultaneously carried out using the chemical properties of the electrolyte. This is one advantage of the HBE sequence system devised as described above. This is because it allows cathodic dissolution of the compound on the cathode side of the HBE and at the same time collection of the precipitate at the terminal cathode and the cathode of the electrowinning system. As shown in the examples below, the present inventors have developed a high-energy titanium metal having a high purity of 99.9% or more and a low oxygen content of 200 ppm or less by using titanium tetrachloride as a raw material. Manufactured in a continuous process with efficiency. For metals that form dendritic precipitates, it may be advantageous to use a terminal cathode with a much larger surface area (approximately 10 times) than that of the HBE to obtain low current densities. Furthermore, by using a power supply that provides oscillating direct current, very low salt dragout is achieved.
−out). A power supply that provides periodically countercurrent current with periodic dead times promotes the formation of smooth deposits. Both the HBE electrolyzer and the sampling electrolyzer can be connected to the same DC power source. However, in actual use, it has been found that it is important to separate the DC supply to the HBE electrolyzer from the DC supply to the metal extraction electrolyzer. For this reason, it is preferred to use two rectifiers. One of the very important applications of the invention is the direct melting of metal ores and the simultaneous electrowinning of pure metals. In particular, oxides, sulfates, sulfides, chlorides, and fluorides can be processed to produce the respective metals. According to the present invention, high-purity product metals can be continuously produced from their compounds. The industrial equipment used for said production can be easily automated. A typical electrolytic cell embodied in the present invention is shown in FIG. The electrolytic cell 300 has four containers 320, 321, 3
It includes a tank 310 made of mild steel that houses 22 and 323. The container is constructed of siliceous refractory material and is inserted into the bottom and placed horizontally. The central containers 321 and 322 are square;
On the one hand, the side containers 320 and 323 are rectangular and half the size of the central container. The central containers 321 and 322 have a groove 325, which allows a vertical wall 330 to be inserted. This wall is also made of siliceous refractory material;
It is held in place by various lids 340. This lid is made of mild steel and covers the tank 310. The walls 330 each have two rectangular openings 3.
31 and 332. That is, one piece 332 is located in the center of the wall, and the other piece 331 is located at the bottom inside the containers 321 and 322. Containers 320, 321, 322, and 323 are filled with molten metal 350, which has a density greater than the density of electrolyte 360. Tank 310 is filled with electrolyte 360 up to opening 332 in wall 330 . A titanium starting sheet is introduced above the side container 320. The activation sheet connects to the cathode terminal of the rectifier. Liquid metal and solid titanium are co-deposited on this sheet. The liquid metal is dripped into container 320 from which it is passed by conduit 351 and pump 355 through metal conduits 357 and 358 to other containers 321,
322 and 323. The metal conduit is coated with a refractory material to ensure electrical insulation. The volatile compound of the reactive metal to be produced (tetrachloride in the case of titanium) is transferred to a mild steel conduit 375.
Supplied by The conduit 375 is connected to the molten metal 35.
In order to dispense the compound inside the containers 321 and 322 filled with 0, their lower ends are bent and a small hole is provided. Containers 321 and 32 into which gaseous compounds are blown
Above 2, a conduit 377 is used for recirculation of the gas. The gas did not react completely and therefore came out of the electrolyte as bubbles. Terminal conduit 358 used to supply liquid metal
is made of graphite and is electrically insulated by being coated with a refractory material only over its length, which passes through the body of the electrolyte. This conduit 358 is connected to the anode terminal of the rectifier and is filled with a container 350 filled with liquid metal 350 to make a suitable electrical connection with the metal itself.
It is immersed in 22. Circulation of electrolyte 360 into and out of the electrolytic cell is via conduits 365 and 366.
It is carried out by. Above the lid 340 of the electrolytic cell 300, suitable devices are shown schematically for the supply 375 and dispersion of gaseous compounds and for the recirculation 378 of the gas coming out of the electrolytic cell, and for the liquid metal 352, respectively. has been done. In a stable state, the electrolytic cell 300 is heated by the Joule effect of the electrolytic current. During start-up, a graphite electrode (not shown) is lowered into the electrolytic cell through an opening in the lid and is supplied with an alternating current to heat and melt the electrolyte 360. FIG. 5 is a schematic cross-sectional view of an electrolytic cell 500, in which only cathodic dissolution of metal compounds is performed. This means that neither simultaneous electrodeposition of the metal to be produced nor reduction of the auxiliary metal takes place. As in FIG. 3 above, inside the containers 520, 521, and 522, the liquid or gaseous compound of the metal to be produced passes through conduits 574 and 575, and the auxiliary metal 550 passes through conduits 557 and 558.
They are each supplied to the HBE through the Walls 530 to circulate the atmosphere in each compartment.
An opening 532 in is near the lid 540 above the level of the electrolyte 560. On the other hand, the circulation of electrolyte 560 in and out of the electrolytic cell is carried out through conduits 565 and 566.
It is done through. FIG. 7 illustrates a cross-sectional schematic diagram of an electrolytic cell 700 for cathodic dissolution of solid metal compounds. In the electrolytic cell, the liquid auxiliary metal 750 only functions as an electronic conductor. The anodic reaction involves a pre-produced portion of the metal, such as titanium metal, for example, in resin form, powder form, or metal shard form, including scrap. This metal is the supply system 752
and is supplied to the inside of the electrolytic cell in a continuous manner through conduit 757. The metal compound is introduced onto the cathode surface of the TBE through conduit 775 with a flow of inert gas 776. Conduits 765 and 766 circulate electrolyte 760 into and out of electrolytic cell 700. Current is supplied to the electrolytic cell by graphite bars 791 and 792. The graphite bar is coated with a refractory material to electrically insulate it from contact with the electrolyte. FIG. 9 is a schematic illustration of a cross-sectional view of an electrolytic cell 900 for cathodic dissolution of solid compounds such as titanium dioxide. In this electrolytic cell, electrolyte 9
Metals lighter than 60% and therefore floating on the electrolyte are used as auxiliary metals. The auxiliary metal is also lighter than the metal compound. When using an electrolyte consisting of fluoride,
A vessel 910 made of mild steel is completely lined with a refractory material 915 to withstand the corrosive effects of the electrolyte. The tank is divided into compartments by walls 930 and 931 of refractory material. The wall 930 is the electrolyte 9
The wall 931 has an opening 932 in its lower part for ion conduction of the electrolyte 960.
Another opening 933 is provided at the top to take advantage of the electronic conduction of the auxiliary metal 950 floating above. Titanium dioxide is fed into the cathode zone of the HBE from above liquid metal 950 by feed conduit 975. Although not shown, a distribution system is installed above the electrolytic cell for supplying the solid compound together with the flow of inert gas and the liquid metal. The liquid metal is supplied by conduit 957. Since walls 931 with electrolyte openings are preferably not used in this embodiment, the circulation of electrolyte into and out of electrolytic cell 900 is carried out by conduit 965.
It is done by. In FIG. 10, an electrolytic cell 1000 for cathodic dissolution of compounds will be schematically explained. In this electrolytic cell, the liquid metal 1050 has the function of electron conduction, while the anodic reaction is gas generation performed on the solid electrode 1095. The solid electrode 1095 is made of graphite, floats on the liquid metal, and is electrically connected to the liquid metal. In FIG. 10, liquid or gaseous compounds are supplied to the electrolytic cell by conduits 1074 and 1075. The use of solid feeds requires a different feeding system. Generated gases such as oxygen, chlorine, sulfur, and others are concentrated in an electrically insulated hood 1096 and directed from the electrolyzer. In FIG. 11, an electrolytic cell 1100 for dissolution and simultaneous electrowinning at a cathode 1170 is schematically illustrated. In the electrolytic cell, the HBE consists of a packed bed 1185 made of graphite on the cathode side, which is placed in a cage 1186 also made of graphite. The cathode side of the HBE is connected to a metal grid 1.
It consists of a graphite plate 1187 enclosed within 188. Both sides of the HBE are made of insulating refractory material walls 11.
30. Wall 1130 has openings 1132 to allow electrolyte 1160 to flow therethrough. The liquid or gaseous compound to be reduced is supplied from below cage 1186 by a curved and perforated conduit 1175, while electrode 1187
At the top, generated gas is led out of the electrolytic cell 1100 through a hood 1189. Another geometry similar to that shown in FIG. 11 consists of another graphite cage instead of the plate electrode for gas generation. The metal is fed in the form of dendrites, fragments or scraps to the anode cage, while the solid compound is introduced into the cathode cage. In FIG. 12, the horizontal geometry for the HBE cell 1200 is shown as consisting of a stack of circular containers. These containers have a pan 122 assembled to allow a rim 1230 of refractory material to be inserted around the periphery.
It is made of graphite in the shape of 0. The refractory material is an electrical insulator and also serves as a spacer for the HBE. Liquid metal 1250 is held within a graphite pan 1220 on the upper side of the container. Cathodic reduction and cathodic dissolution of the compound takes place at the bottom 1280 of the vessel. The gaseous or liquid compound is
Each conduit 12 in each HBE
74. Conduit 1257 supplies liquid metal to the container. A flow of electrolyte 1260 enters the cell through conduit 1265 and exits the cell through conduit 1266. FIG. 14 is a simplified flow chart outlining the materials and energy for an industrial apparatus for electrolytic titanium production using liquid metal and titanium tetrachloride as feedstock. The apparatus consists essentially of (1) a melting electrolyzer "D _" of the type shown in FIG. Electrowinning electrolytic cell "E" in which titanium and auxiliary metals are co-deposited with
It consists of and. The melting electrolyzer has the purpose of cathodically reducing Ti() to soluble titanium(), while the anodic reaction involves auxiliary metals. In the extraction electrolytic cell, two metals, solid Ti and liquid auxiliary metal, are co-deposited on the cathode. In the figure, continuous lines indicate the flow of matter, and broken lines indicate the flow of energy. The meanings of the symbols are as follows. EVS: Energy for evaporating and superheating _TiCl4 . ED: Energy for electrolysis in the melting electrolyzer. EE: Energy for electrolysis in the extraction electrolyser. EP: energy for deposition equipment and heat losses l: liquid v: vapor Me: liquid auxiliary metal e: electrolyte VS: evaporator and superheater D: electrolytic melting cell E: electrowinning cell between two electrolytic cells There are three flows of matter. These are: the electrolyte circuit from electrolytic cell D to electrolytic cell E, the return circuit from E to D and the auxiliary metal flow from electrolytic cell E to electrolytic cell D. The Ti concentration difference between the incoming and outgoing electrolytes is maintained at about 10-15% with a flow of electrolyte between the electrolytic cells at a capacity of about 3 electrolytic cells per hour. The generated chlorine will be reused. All operations are preferably carried out under a controlled atmosphere in which the partial pressures of oxygen, nitrogen and water vapor are kept at the lowest practical values. The device of the invention is therefore constructed indoors, isolated from the outside environment. Example 1 Continuous production of electrolytic titanium in an apparatus according to the flowchart outlined in FIG. 14, using titanium tetrachloride as raw material and lead as auxiliary metal, in a melting electrolytic cell as shown in FIG. 5. Operating data: Titanium production: 4.16 Kg/hr Titanium tetrachloride feed: 16.65 Kg/hr Electrolyte flow rate: 610 Kg/hr Electrolyte average temperature: 775°C Chemical properties of the electrolyte leaving the melting electrolyzer (weight %): NaCl: 69.9% TiCl _x : 26.0% (Ti10.5%) PbCl ₂ : 4.1% Average valence of Ti: 2.05 Melting electrolyzer: Voltage: 2.2V Current: 1618A Collection electrolyzer: Voltage: 4.5V Current :10354A Example 2 Titanium dioxide as raw material (containing TiO ₂ 98%)
Continuous production of electrolytic titanium using a lithium-sodium alloy as the auxiliary liquid metal, in a melting electrolyzer as shown in FIG. 9, in an apparatus according to the flowchart outlined in FIG. 14. Operating data: Titanium production: 3.13 Kg/hr Dioxide feed: 5.44 Kg/hr Electrolyte flow rate: 1130 Kg/hr Average temperature of the electrolyte: 725°C Chemical properties of the electrolyte leaving the melting cell (weight) %): Soluble titanium (as Ti ⁺⁺⁺ ): 2.3% Lithium fluoride and sodium fluoride (50% eutectic) Melting electrolytic cell: Voltage: 2.9V Current: 649A Collection electrolytic cell: Voltage: 5.0V Current: 7790A

[Brief explanation of drawings]

1 to 13 are cross-sectional views of various electrolytic cells according to preferred embodiments of the present invention. 1st
FIG. 4 is a schematic flowchart of the electrolytic titanium manufacturing apparatus of the present invention.

Claims (1)

[Scope of Claims] 1. A method for producing a metal or metalloid from a metal or metalloid compound using an electrolytic cell comprising an anode, a cathode, and an electrolyte extending from the anode to the cathode, the method comprising: in electron conductive contact with a cathode and solubilized in an electrolyte by direct cathodic reduction; (a) said electrolytic cell is charged with an auxiliary metal or mixture of metals in solid or liquid state; (b) providing a plurality of bipolar electrodes, each charge consisting of an anode portion and a cathode portion; (b) passing the compound to be solubilized into the electrolytic cell while passing an electric current through the electrolytic cell; providing direct cathodic reduction of the metal or metalloid of the compound on the cathode portion and the metal from the anode portion of the respective charge into the electrolyte; and (c) circulating an electrolyte in a closed circuit including the electrolytic cell and the electrowinning cell, and electrolytically separating the metal or metalloid to be produced in the electrolytic cell from the electrolyte. The method, characterized in that: 2. Process according to claim 1, characterized in that the auxiliary metal in each charge is different from the metal to be produced. 3 The auxiliary metal or mixture of metals in each charge shall be
2. Process according to claim 1, characterized in that it consists of the metal to be produced. 4. Claim 1, characterized in that the charge is a pool of auxiliary metals or mixtures of metals that are more or less dense than the electrolyte,
The method described in Section 2 or Section 3. 5 (a) the temperature of the electrolyte is below the melting point of the metal or metalloid to be produced, and (b) the metal or metalloid is separated in an electrowinning cell as a solid deposit with a quantity of auxiliary metal in a liquid state. , and the auxiliary metal thus separated is collected in liquid state and recycled to the pool in the electrolytic cell.
The method described in section. 6. Process according to claim 5, characterized in that the electrolyte is a molten salt bath at an elevated temperature and the auxiliary metal or metal mixture is in a molten state at said temperature. 7 The amount of metal or metalloid to be produced is deposited in solid state on the cathode of the electrolytic cell together with the amount of auxiliary metal in liquid state, and the auxiliary metal thus separated is collected in liquid state to form a pool with the cathode. 7. A method as claimed in claim 5 or claim 6, characterized in that the method comprises the steps of: recirculating the bipolar pools from there into one of the bipolar pools; 8. characterized in that the pool forms the cathode and the compound to be solubilized is fed to this pool, thereby cathodically solubilizing the compound,
A method according to claim 7. 9. The method according to any one of claims 1 to 5, wherein the electrolyte is an aqueous solution. 10. Process according to any one of claims 1 to 8, characterized in that the compound to be solubilized is titanium tetrachloride and the auxiliary metal is lead. 11. Process according to any one of claims 1 to 8, characterized in that the compound to be solubilized is titanium dioxide and the auxiliary metal mixture is a lithium/sodium alloy. 12. The method according to any one of claims 1 to 5, wherein the electrolyte is a non-aqueous solution. 13. Process according to any one of claims 1 to 8, characterized in that the compound to be solubilized is titanium tetrachloride. 14 Claims 1 to 1, characterized in that the compound to be solubilized is zirconium tetrachloride.
The method according to any one of Section 8. 15. Process according to any one of claims 1 to 8, characterized in that the compound to be solubilized is titanium dioxide. 16 Claims 1 to 3, characterized in that the compound to be solubilized is zirconium dioxide.
The method according to any one of Section 8. 17 The metal or metalloid to be produced is boron,
9. A method according to any one of claims 1 to 8, characterized in that sulfur, arsenic, antimony or silicon is used. 18. The method according to any one of claims 1 to 8, characterized in that metals such as lead, copper, tin, and zinc are produced. 19. According to any one of claims 1 to 8, which is characterized in that it produces metals such as titanium, zirconium, hafnium, tantalum, niobium, vanadium, chromium, molybdenum, tungsten, manganese, and aluminum. Method described. 20. The method according to any one of claims 1 to 8, characterized in that ferroalloys such as cobalt iron, nickel iron, ferromanganese, ferrovanadium, ferrosilicon, and ferrochrome are produced. . 21. Characterized by producing metals such as bismuth, cadmium, beryllium, rare earth metals, etc.
A method according to any one of claims 1 to 8. 22. Claim 1, characterized in that the hybrid bipolar electrode is solid and is produced as a structure formed by pressing and spreading a paste of the compound of the metals to be produced on an auxiliary metal and applying pressure. - The method according to any one of clauses 8 to 8. 23. The method according to any one of claims 1 to 8, characterized in that a transition metal is produced.